Separation of tertiary base olefins from hydrocarbon mixtures



1945- D. E. BADERTSCHER arm. 2,386,773

SEPARATION OF TERTIARY BASE OLEFINS FROM HYDROCARBON MIXTURES Filed April 4, 1944 R Baderficfier INVENTO Patented Oct. 16, 1945 SEPARATION OF TERTIARY BASE OLEFINS FROM HYDBOCARBON MIXTURES Darwin E. Crowley, Thorofare. N. J.,

New York Badertscher, Woodbury, Duncan J. Penna Grove, and Charles F. Feasley, assignors to Socony-Vaouum Oil Company, Incorporated,

a corporation of Application April 4, 1944, Serial No. 529,484

17 Claims.

This invention has to do with a selective method for effecting the separation of certain olefins from hydrocarbon mixtures. More specifically, the present invention has to do with a vapor phase, catalytic treatment of a hydrocarbon mixture with H28 whereby only those R:C=C-/ wherein R is a low molecular weight alkyl group such as methyl, ethyl, etc. Typical members of this class, and preferred herein, are isobutylene (H3C):C=CH2, and trimethyl ethylene,

n (HiC):C=C

For some time, considerable attention has been directed to the problem of separating the various types of hydrocarbons from hydrocarbon mixtures. One such problem has been that of separating one or more of the tertiary base oleflns from hydrocarbon mixtures. For example, the problem of separating isobutylene, a tertiary base olefin from a mixture of C4 hydrocarbons has been approached from several directions; yet with one possible exception (discussed hereinaiter) none of the approaches previously made has been at all satisfactory. The obvious method, namely, fractional distillation, is extremely laborious and time consuming in view of the relatively narrow boiling range of the several C4 hydrocarbons, as shown below:

0. hydrocarbons 35 95 51 2 2 5,

lsobutane -l2. 4

Another physical method resorted to for separating oieflns from saturates involves the use of various azeotropic distillation procedures.

While such methods have been successfully used to separate olefins from saturates, they have not been so specific as to separate tertiary base olefins from other oleilns, normal or secondary. The same can be said for solvent extraction methods. In short, physical methods have not proven to be sufficiently selective for tertiary base oletlns.

Chemical procedures have also been proposed for the separation of olefins from saturates and some of these have been somewhat specific for the separation of tertiary base olefins from other olefins. One such procedure (referred to hereinabove) which has been applied commercially, is based upon the tendency of isobutylene to be selectively absorbed by -10% sulfuric acid at room temperature. In said procedure, isobutylene is thereafter expelled from the acid when the acid is heated. This procedure is characterized, however, by some undesirable features; for example, an appreciable portion of the isobutylene is lost through polymerization, and normal butenes-in the presence of isobutylenealso tend to be absorbed by the same acid, in

' which case the regenerated isobutylene is contaminated with normal butenes. Another chemical method which has been proposed involves the selective alkylation of phenols by tertiary olefins in the presence of certain catalysts. In the latter process, phenols are alkylated by isobutylene and substantially all of the remaining C-l hydrocarbons do not so alkylate the phenols. The tertiary phenols are subsequently heated in the presence of a catalyst whereupon isobutylene is regenerated.

As will be apparent from the following, the present invention involves the second general type of approach to the problem of separating tertiary base olefins from hydrocarbon mixtures, namely, a chemical method.

We have discovered that a tertiary base olefin contained in a hydrocarbon mixture can be separated therefrom in a substantially pure condition by means of the following new and novel method. A hydrocarbon mixture containing a tertiary base olefin is first treated with H28 in the vapor phase and in the presence of a catalyst at a well-defined temperature as hereinafter described, whereupon only the tertiary base olefin in said mixture is converted to its corresponding tertiary mercaptan, the other hydrocarbons in said mixture not being so converted; the said tertiary mercaptan contained in the reaction mixture obtained by the initial operation is then separated therefrom; and the said tertiary mercapdividually or collectively,

tan is heated alone or in the presence of a catalyst of the type used in the initial treatment, at a temperature in excess of the optimum temperature for the first-mentioned operation, as hereinafter described, whereupon the said mercaptan decomposes to the corresponding tertiary base olefin and hydrogen sulfide, and said olefin is iso lated in a substantially pure statF-and H28 is recovered for reuse.

It will be understood that a hydrocarbon mixture containing more than one tertiary base olefin can be similarly treated. In such case, the corresponding tertiary mercaptans formed in the above-described initial operation can be separated i'rom the reaction mixture and heated inwith or without said catalyst, at a temperature in excess oi. the optimum temperature for the initial operation. When the tertiary mercaptans are heated together in the last-mentioned operation, it will be clear that the corresponding teritary base oleflns will be formed and that said olefins can be readily separated from each other by any one of a number of available separation procedures, such as fractional distillation, fractional crystallization, etc. Similarly, the tertiary mercaptans obtained from the initial operation can be separated from each other and heated individually as indicated above.

It is well known to those familiar with the art that olefins will react with H23 in the presence of various catalysts to form mercaptans. For example, it has been suggested that olefins of at least eight carbon atoms will react with H28 in the liquid phase in the presence of certain catalysts, at time intervals oi from 6 to 72 hours, to form sulfur-containing compounds including sulfides and mercaptans. In the present invention, the initial treatment of a hydrocarbon mixture containing one or more tertiary base oleflns with H25 in the presence of a catalyst distinguishes over the foregoing procedure, in that said treatment is carried out in the vapor phase with a comparatively short contact time which may vary from a, fraction of a second to several minutes. Another fundamental distinction between previously proposed processes for the conversion of olefins to mercaptans, and the initial operation of the present invention is predicated upon our discovery that this catalytic treatment is selective for the conversion of certain olefins to their corresponding mercaptans. That is, in this initial treatment, only the tertiary base olefins, typified by the C4 and Cs tertiary base" olefins, isobutylene, trimethyl ethylene, and 2-methyl butene-l, contained in a mixture of hydrocarbons are converted to their corresponding tertiary mencaptans when the hydrocarbon mixture in the vapor phase and in admixture with HzS is passed over a suitable catalyst with the temperature of the catalyst or reaction zone maintained within certain preferred limits, depending upon the nature of the catalyst, the pressure in the reaction zone, etc. This initial operation, namely, the selective catalytic conversion of tertiary base olefins to their corresponding mercaptans, is more fully discussed in co-pending applications Serial No. 461,116, filed October 7, 1942; Serial No. 474,924, filed February 6, 1943; and Serial Nos. 492,669 and 492,670, filed June 29, 1943; in all of which two oTThe present inventors, Darwin E. Badertscher and Duncan J, Crowley, are co-inventors.

The catalysts which have been found to be efiective for the purpose of selectively converting tertiary base olefins to their corresponding mercaptans are the following: acids and thioacids of is from about 55 C.

. genated acids, such phosphorus and their anhydrides and thioanhydrides, elementary (red) phosphorus, sulfuric acid and organic sulfonic acids, non-plastic clay-type catalysts typified by fuller's earth, alumina-silica type synthetic catalysts, tungstic acid and haloas trichloracetic, etc. Thus the catalysts useful forthe present invention are those which will promote the conversion of a tertiary base olefin with hydrogen sulfide to the corresponding tertiary mercaptan under the conditlons defined herein. For the purposes of the present invention, preference is given herein to the acids and thioacids of phosphorus and their anhydrides and thioanhydrides, representative of which are HaPO4, HaPOa, P205, P203, H:PS4, P285, etc; particular preference being given to phosphoric acid. There is little, if any, diminution in the effectiveness of our preferred catalysts as used herein. Naturally, the presence of appreciable amounts of moisture in the reactants would tend to leach out water-soluble catalysts such as phosphoric acid. Therefore, it is desirable to dry the gases prior to contacting them with the catalyst. The drying of the gases prior to introduction into the reactor presents no difllculties and is routine procedure to those familiar with the chemical and petroleum arts. Depending upon the physical properties of the phosphorus compound, the catalyst may be used alone (particularly if comprised of solid particles) or adsorbed on the surface of a suitable inert carrier, the latter form being preferred.

As indicated above, the method contemplated herein involves a subsequent treatment of the tertiary mercaptan (or tertiary mercaptans) obtained in the initial operation, such that said mercaptan (or mercaptans) is decomposed or converted back to the corresponding tertiary base ole fin (or oleflns) and Has. It will be clear from the foregoing that this subsequent treatment or operation follows a separation operation in which the tertiary mercaptan (or mercaptans) is separated from those hydrocarbons which are contained in the hydrocarbon mixture (subjected to the initial operation) and which are not converted to their corresponding mercaptans by said treatment; such hydrocarbons include normal olefins, secondary olefins, diolefins such as butadiene, cyclic olefins, acetylenes, saturated hydrocarbons, aromatics, heterocyclics, etc.

One of the most important factors in the method contemplated herein is temperature control. As discussed in the aforementioned co-pending applications, the reaction Of hydrogen sulfide with a tertiary base olefin to form a tertiary mercaptan in the presence of one or more of the aforesaid catalysts, is quite sensitive to temperature. For example, it was effectively shown in application Serial No. 461,116, that the operative temperature range with a catalyst selected from the group consisting of acids and thioacids of phosphorus and their anhydrides and thioanhydrides, is from about 25 C. to 175 C., and that the optimum temperature with such a catalyst is in the neighborhood of 75 to C. Similarly, it was shown in application Serial No, 474,924, that the operative temperature range with nonplastic clay-type catalysts, such as fullers earth, to about 200 0., and the optimum temperature, as above, is of the order of 75-80 C. In the same manner, it was shown in application Serial No. 492,669 that the operative temperature range with elementary phosphorus as the catalyst is from about 25 C. to about 200 C., and the optimum temperature is asseyvs at about 55" C. correspondingly, when organic sulionic acids and sulfuric acid are used as cattertiary base mercaptan is caused to revert to the corresponding tertiary base olefin is greater than the optimum temperature for the synthesis or th said mercaptan. Thus when the same catalyst is used for the reversion oi the mercaptan to the corresponding tertiary base olefin, the following relationships will be noted: when the catalyst is one selected from the group consisting of acids and thioacids oi phosphorus and their anhydrides and thioanhydrides, the temperature necessary for the reversion of the tertiary mercaptan to the corresponding tertiary base olefin will be greater than 75-80 0., which is the optimum temperature shown in application Serial No. 461,116, and will preferably be greater than about 150 0. As will appear from the data presented hereinaiter, a temperature of about 230 C. is particularly effective for this operation when phosphoric acid is used as the catalyst. With regard to the other catalysts referred to above in connection with the aforesaid co-pending applications: temperatures greater than about 80 0. should be used with fullers earth; greater than about 55 C. with elementary phosphorus; and greater than about 75 C. with organic sulfonic acids and sulfuric acid. It will be apparent that the temperature used for this operation should not exceed that temperature at which the isobutylene-or other tertiary base olefin-so produced would tend to decompose to other products.

As pointed out hereinabove, the operation in which a tertiary mercaptan is decomposed to the corresponding tertiary base olefin may also be a thermal operation in which no catalyst is used. Although the temperatures for this thermal operation are substantially higher than for the above-described catalytic operation, the yield oi. tertiary base olefin is generally higher than when one oi the aforesaid catalysts is used. This may, perhaps, be due to a relatively greater degree of polymerization when one of said catalysts is used. It may be said that the minimum temperature for the thermal operation should not only be greater than the optimum temperature at which the tertiary mercaptan is formed in the initial operation, but it should also be greater than the maximum temperature effective in said initial operation. In general, then, temperatures greater than about 150 C. should be used, and preferably temperatures of the order of 300 to 450 C. It will also be apparent that the temperatures used in the thermal decomposition of said tertiary mercaptan should not be so great as to cause the decomposition of the corresponding tertiary base olefin so formed.

Not only is a tertiary base olefin, contained in a hydrocarbon mixture. converted to the corresponding tertiary mercaptan when said mixture is treated with H38 in the presence of one or more of the foregoing catalysts, but a portion of said olefin is also converted to the corresponding sultide and other sulfur-containing products and to the corresponding dior poly-oleflns. For example, when a hydrocarbon mixture containing isobutylene is so treated. a predominant proportion of said isobutylene is converted to tertiary butyl mercaptan, smaller proportions also being converted to such products as tertiary butyl sulfide (HsClaC-S-CWHD: and di-isobutylene. These materials, the sulfides and dior poly-oleiins corresponding to the tertiary base oleflns present in the original hydrocarbon mixture, have also been found to respond to the subsequent thermal or catalytic treatment, thus yielding pure lsobutylene. As will appear hereinafter in discussion of illustrative data, the temperatures at which such materials decompose or revert to the corresponding tertiary base olefin are somewhat higher-generally, about 100 C. higher-than those at which the related tertiary mercaptans decompose. It is to be understood. therefore, that such intermediate products are contemplated as desirable sources for the-obtainment of substantially pure tertiary base oleiins, in addition to the related tertiary mercaptans.

It will be apparent to those skilled in the art that the decompositions or reversions of the aforesaid tertiary mercaptan, sulfide and tertiary base olefin p lymers to the corresponding tertiary base olefin, may be represented by the following relationships in which isobutylene and the aforesaid derivatives thereof are chosen for the purposes oi illustration.

wherein X is a whole number.

Obviously, the mercaptan shown as formed in (2-D) above can undergo decomposition to iso-- be employed in practicing the process of this invention; and Figure 2 is a sectional elevation showing in enlarged detail a typical form of reactor which may be employed in the system shown in Figure 1.

In Figure 1, reference numeral il indicates a reactor which is shown in Figure 2 as embodying a shell I! which may be of circular or other suitable cross-sectional shape, such shell being provided near its top with a partition plate i3, having a plurality of openings I, which receive the upper ends of tubes l5 secured therein in any suitable manner. such as welding (not shown). The lower ends of the tubes 15 are supported in openings it through a bottom partition plate ll secured near the bottom of the shell I! in any suitable manner so as to form a chamber II in the shell between plates l1 and I8. For the purpose oi controlling the temperature within the tubes it. a suitable heat exchange medium is circulated through the chamber II from an inlet 20 toanoutletll.

The top oi the chamber or shell I! is provided with a cover 2!, which with the top partition plate it forms a chamber 23 in the top of the shell adapted to receive reaction vapors through an inlet 24, which vapors enter the various tubes from the chamber 23, as indicated by the arrows. The bottom oi the shell I! is provided with a bottom cover 26, through which the products of reaction pass from the tubes ll into the product outlet 16.

The bottoms of the various tubes I! are provided with a suitable mesh material to support a body catalyst indicated by the stlppling in Figure 2 within these tubes. This mesh material may be supported in any suitable manner and, as shown in Figure 2, comprises a screen supported beneath the bottom plate II by a similarly perforated plate iI'.

As aforesaid, the reaction contemplated herein is quite sensitive to temperature control; and although the length and size of the reaction tubes II and the relation between the total volume of the chamber l8 and the volume within such chamber which is occupied by the reaction tubes may be varied over relatively wide limits, it is to be understood that the relationship between these various factors, the temperature of the heat exchange medium, and the rate at which heat exchange medium is circulated through the chamber It should be so adjusted as to maintain the temperature in the reaction zones of the various catalyst tubes l5 within the range for most emcient operation, as will be hereinafter discussed.

Referring back to Figure 1: reference numeral 30 indicates a conduit adapted to carry hydrocarbons through a meter M into the reactor inlet conduit 24. This conduit is shown as passin through a pre-heater or vaporizer 3|, through which a hot heat exchange medium is circulated by means of connections 32 and 32'. Hydrogen sulfide is introduced into the system through the valve 34, conduit 35 and a meter M, such hydrogen sulfide being optionally introduced into the inlet 24 on either side of the vaporizer 8| by means of valved connection 38 or 38.

With regard to the pre-heater or vaporizer 3 I it is to be understood that other suitable means may be provided for insuring that the reactants are in the vapor phase when they pass into the catalyst tubes in the reactor. For example, it may be found, particularly after the reaction has been started, that there is suflicient heat in the reactor itself to effect this vaporization, or heater coils may be provided in the chamber 23, as will readily appear to those skilled in the art.

Suitable means for controlling the temperature of the heat exchange medium entering the reactor through inlet 20 are indicated by reference numeral 40. The temperature-control means 40 may be any suitable heat exchange device and can be either manually or automatically operated in any manner well known to those skilled in the art. Also, if desired, the heat exchange medium may be recirculated from the outlet 2! through the temperature control 40 to the inlet 20 as will also be obvious to those skilled in the art. Any suitable heat exchange medium, such as water, may be employed to control the temperature in the chamber III or reactor ll.

Reference numeral 4| indicates a cooler or condenser through which the product-outlet con.

assume duit I4 into conduit section I4, which opens into a sealed receiving chamber 21. The cooler or condenser 4| is provided with an inlet 42 equipped with temperature-controlling means 48 and with a heat exchange medium-outlet section 44. The temperature oi the cooler 4| ma be controlled through the controlling means 43 so as to condense substantially all oi the mercaptan which can then be withdrawn together with the higher boiling products (included among which are the sulfide and the polymers or the tertiary base olefin) of reaction from the sealed chamber 21 through a valved liquid-outlet connection 4! to conduit which is provided with an adjustable valve BI, and which connects with a second reaction chamber or reactor ll wherein the mercaptan and higher boiling products are decomposed to the corresponding tertiary base olefin; or, such temperature in the cooler 4| may be controlled so that only the high boiling prodnets are condensed. substantially all or the mercaptan together with the hydrogen sulfide and hydrocarbon gases being conducted in such case trom the sealed chamber 21 through a Vaporoutlet conduit 46, valve 41 and conduit 48 to the bottom of a scrubbing tower 49.

The top of the scrubbing tower 48 is provided i with a gas vent 50 and an inlet conduit II for a scrubbing solution such as aqueous caustic soda, The bottom or the scrubber 48 has an outlet 62 which connects with the bottom of a still or stripper 54, the outlet 52 being equipped with a drainage valve 53. The still or stripper i4 is shown as being equipped with a high-pressure steam coil or other suitable source of heat it and has an outlet It which connects through a condenser I! with a separator 58. The separator 58 is provided with a valved mcrcaptan outlet 59, a sight glass 60 to facilitate removal of mercaptan and a valved water outlet 6|. The water outlet Bi connects through a valve 82 with a water return pipe 68, which in turn is shown as connecting with the caustic reservoir 41. The still 54 is shown as being equipped with a caustic outlet conduit 54 which includes a liquid caustic well 84', the purpose or which is to prevent mercaptan vapor from leaving still 54 by the conduit 64. Caustic solution passes through conduit 64 to a caustic cooler 65 and exits therefrom through outlet 86 to the caustic reservoir 41. The caustic reservoir is fitted with a drainage means 88. The caustic reservoir is also equipped with a conduit ill which connects with the intake side of a pump I0. The discharge side of pump III is shown as connecting with inlet conduit ii of scrubber 49. Means indicated at H are provided for adding fresh caustic. and means indicated at 12 are provided for adding fresh water to the system when desired. A water drain is shown at 13, and the last-described connections are shown as being provided with suitable valves for controlling the addition or discharge of the various media.

The second reactor is shown as connecting with conduit 82 which carries mercaptan from the separator 58 or carries high boiling reaction products, with or without said mercaptan, from the sealed reservoir 21 to a second preheater or vaporizer II and conduit 84. The preheater or vaporizer i3 is similar to the preheater II described above, and the reactor 45 may be the same as reactor ll (Figure 2) already described. As indicated above, however, the reactor 88 may be void of catalyst in which case it is preferably comprised of reactor tubes 15 (in Figure 2) containing inert solid particles as a contact medium.

assavvs Reactor it is equipped with suitable means for controlling the heat exchange medium enter-s ing the reactor through inlet as and exiting through outlet 01, such means being indicated by reference numeral 80. Temperature control means is similar to the temperature control means 00 referred to hereinabove and contains a suitable heat exchange medium.

Reierence numeral 90 indicates a cooler or condenser through which the product flows from reactor 85 and reactor outlet 0|. Cooler 00 is provided with a heat exchange medium-inlet 82 equipped with a temperature control means 00 and with a heat exchange medium-outlet connection oz. The product cooled in the cooler 00 passes through the conduit 94 into a cold reservoir which is equipped with a valved liquid outlet connection 06 through which condensed high boiling products and undecomposed mercaptan can be withdrawn. The reservoir 00 is also equipped with a vapor conduit outlet 01 through which tertiary base olefin and hydrogen sulfide flow into a hydrogen sulfide separator 00.

The separator 08 is provided with an inlet conduit 09 for a solution such, for example, as aqueous tri-potassium phosphate which removes hydrogensulfide present in the vapor entering the separator. The bottom of the separator 08 has an outlet I00 through which the solution such as aqueous tri-potassium phosphate and hydrogen sulfide in the form oi potassium acid sulfide is removed. The top of the separator 90 is provided with a vapor conduit IOI through which tertiary base olefin and any'unchanged tertiary mercaptan pass. The vapor conduit IOI connects with a scrubber I02 which is provided with an inlet conduit I00 for a scrubbing solution such as aqueous caustic soda which removes traces of inercaptan present in the vapor entering said scrubher. The bottom of the scrubber I02 has an outlet I04 through which aqueous caustic soda, taining some tertiary mercaptide, is removed.

The top of the scrubber I02 is provided with a vapor conduit I00 through which tertiary base olefin passes. The vapor conduit l0 connects with the drier I 05 containing a suitable drying medium such as calclumcloride, and the drier I0! is in turn connected with a condenser (or compressor) I01 through conduit I00. The condenser I01 is also attached. through conduit I00, to a storage reservoir I09 which is equipped with a valved liquid outlet "0 and with a valved vapor outlet III, the latter outlets being means for withdrawing substantially pure tertiary base olefin from the system.

In practicing a preferred form of the present invention with apparatus of the type shown in Figures 1 and 2, a hydrocarbon mixture containing a. tertiary base olefin, and hydrogen sulfide are metered 'into the system through meters M and M, respectively. The proportions of these two reactants may be varied over relatively wide limits, but for optimum results it is preferred that these proportions be such that the hydrogen sulfide be slightly in excess of the molar equivalent required to react with the tertiary olefin which is present.

The admixture of hydrocarbon and ms is introduced into the reactor II in the vapor phase, as by first passing the hydrocarbon through the vaporizer ill prior to admixture with H28. Upon entering the reactor II, the hydrocarbon-H28 vapor mixture passes through the catalyst tubes I5 where'it contacts the catalyst for a short period of time. Itis an important feature of the method that the period of catalyst contact is comparatlvely short. with a catalyst of the type described herelnabove, contact times of from about a fraction of a second to several minutes serve the purposes oi the present method. but in general. a contact time or a few seconds to 2 or 3 minutes is preferred. The temperature of the heat transfer medium in chamber I0 is controlled by the temperature control means 40 so that the temperature oi. the catalyst zone within the tubes II is maintained within the range that will give the desired conversion. As aforesaid, the selective conversion of a tertiary base olefin to the corresponding tertiary mercaptan is quite sensitive to temperature, and i'or this reason the temperature of the catalyst zone should be carefully controlled.

When in contact with the catalyst in the catalyst tubes I5 under the conditions described herein, the-tertiary base olefin reacts with the hydrogen sulfide in the reaction mixture to form the corresponding tertiary mercaptan. By way of illustration, when the tertiary base olefin present in the original hydrocarbon mixture is isobutylene, tertiary butyl mercaptan is formed and also a small amount of higher boiling materials which are predominantly comprised of tertiary butyl monosulfide and di-isobutylene. Other hydrocarbons present in the original hydrocarbon mixture do not so react with the hydrogen sulfide and pass through the catalyst zone substantially unchanged. Thus, the eiliuent gases leaving the reactor II through discharge conduit 28 contain tertiary butyl mercaptan, high boiling materials including tertiary butyl mono-sulfide and di-isobutylene. unreacted hydrocarbons (other than isobutylene or other tertiary base olefins) and unreacted Has. As indicated above, the unreacted hydrocarbons'present in the chinent gases may include normal olefins, secondary oleflns, saturated hydrocarbons and others as indicated hereinabove.

' The eilluent gases flow through the discharge conduit 26 to the condenser I I. As aforesaid, the temperature 0! the condenser may be maintained such that only the high boiling products are condensed, in which case, the condensate flows into the sealed chamber 21, from which it can then be withdrawn through the valved outlet connection 45. The condensate may be so withdrawn and carried through the conduit 00 to the second reactor as described hereinafter. The unreacted hydrocarbons, unreacted H28 and tertiary butyl mercaptan are not condensed when such a temperature is maintained in the condenser II, and

fiow through the vapor-outlet conduit 46.

The preferred procedure for separating the tertiary butyl mercaptan from unreacted hydrocarbons and unreacted H28, in conduit 00, involves a scrubbing treatment. The vapors in conduit 0 flow through the valve 41 and conduit 40 to the bottom of the scrubbing tower 40. The vapors rise in the scrubber l0 and contact a downstream of scrubbing solution, such as aqueous caustic soda whereupon tertiary butyl mercaptan and hydrogen sulfide are converted respectively to the corresponding soluble alkali mercaptlde and alkali sulfide or hydrosulflde. The unreacted hydrocarbons are unaffected by the caustic soda and are removed through the gas vent 50 from which they may be conducted to through the outlet connection 52 to the still High-pressure steam or other heating medium passes through the coil 55 in the still 54, thereby heating the caustic solution to an elevated temperature. On heating the caustic solution, the alkali mercaptide is converted to the corresponding tertiary butyl mercaptan which, along with some water, distills from the solution. The tertiary butyl mercaptan-water vapors rise to the outlet 56, flow therethrough to the condenser 51 where they are condensed and from which the condensate flows to the separator 58. The condensate separates herein (58) into an upper layer of tertiary butyl mercaptan, and a lower layer of water. The mercaptan layer is withdrawn through the valved outlet 59, a sight glass 60 being provided to facilitate the mercaptan withdrawal.

The lower water layer is allowed to drain from the bottom of the separator, through the valved water outlet 6|. It is recombined, in passing through the valve 62 and the water-retum pipe 63, with the caustic solution which has been discharged from the still 54. This caustic solution has passed through conduit 64, well GI, the cooler 65 and conduit 65 to caustic reservoir 61. This cold caustic solution, which contains some alkali sulfide, combined with water from the separator 58, is pumped by means of the pump HI to the caustic scrubber 49 through the inlet H. If, however, said caustic solution from the still 5! tends to accumulate an appreciable amount or alkali sulfide, it can be removed from the system by means of the drain 68, and can be replaced with a desired amount of fresh caustic through the means II. This is necessary when a substantial amount of unreacted H28 is present in the e1- fiuent gases from the reactor ii and reacts with caustic soda in the scrubber 49 to form alkali sulfide; I! it is necessary to introduce additional water into the system to add to the caustic solution cooled in the cooler 85, fresh water can be introduced through the means I2.

Now, the tertiary butyl mercaptan alone, as taken from the separator 58 and valved conduit 59, or together with higher boiling products taken from the reservoir 21 and line 80, is suitable for further treatment. The charge taken through conduit 82 is carried to a preheater 8: wherein it is vaporized. The vapors in the preheater 83 pass through the preheater outlet 84 to the reactor 85, where they are subjected to the elevated temperature conditions prevailing therein for a relatively short period 01 time, preferably from about several seconds to several minutes. The temperature of the heat transfer medium of reactor 85, entering through line 86 and exiting through line 81, is controlled by the temperature control iill so that the temperature of the reactor 85 is maintained within the range that will give the desired decomposition, as discussed hereinabove and as illustrated below.

when in the reactor 85 under the conditions described herein, the tertiary butyl mercaptan decomposes to isobutyiene and hydrogen sulfide.

"I! higher boiling materials such as tertiary butyl monosulfide and di-isobutylene are also present in the vapors, they also will be decomposed to isobutyiene and hydrogen sulfide in accordance with the equations shown above. The eiiiuent gases flow through the discharge conduit ii to the condenser 90 wherein any undecomposed mercaptan and higher boiling products are condnsed. The condensate flows into the chamber 85, from which it can be withdrawn through the outlet connection 96. It will be obvious to those skilled in the art that the condensate removed through the outlet connection 98 can be reintroduced in the reactor by any suitable means (not shown), such as by a connection with conduit 82.

The uncondensed portion of the decomposition mixture flows through the vapor outlet 91 (01' the chamber to the bottom of a separator 98. This uncondensed portion, predominantly comprised oi isobutylene and hydrogen sulfide, and possible traces of undeoomposed mercaptan, rises in the separator 98 and contacts a, downstream of a solution, such as aqueous tri-potassium phosphate whereupon hydrogen sulfide is converted to the corresponding potassium acid sulfide. The isobutylene and undecomposed mercaptan, it present, are unafiected by the aqueous til-potasslum phosphate and are removed through the vapor outlet iiH from which they pass to the bottom of a scrubber I02. Isobutyiene and undecomposed mercaptan, if present rise in the scrubber I02 and contact a downstream of scrubbing solution such as aqueous caustic soda whereupon undecomposed mercaptan is converted to the corresponding mercaptide. The isobutylene is unaffected by the caustic soda in the scrubber ill! and is removed through the vapor outlet I from which it passes through a drier ")5, which contains a suitable drying medium such as calcium chloride, etc. From the drier I", substantially pure isobutylene flows through conduit I06 to a condenser Ill! and then through the condenser outlet Illa to a sealed storage chamber Hi9. Isobutyiene may be withdrawn from the sealed chamber I08 as a liquid through the valved outlet "0, or as a vapor through the valved outlet I I.

The aqueous tri-potassium phosphate containing potassium acid sulfide taken from the H23 separator 88 through the outlet I00 may be taken to a suitable still (not shown) where the solution may be heated and hydrogen sulfide regenerated therefrom. The hydrogen sulfide thus obtained may be used again in the process, entering as through valved conduit II. The regenerated aqueous tri-potassium phosphate may also be used again and introduced into conduit 89. Similarly, the caustic soda solution containing alkali mercaptide taken from scrubber I02 through outlet may be taken to a still (not shown) such as the still 54 previously described. In the still, the alkali mercaptide is converted to the corresponding tertiary mercaptan and introduced in the process as through conduit 82 (connecting means not shown).

It will be understood, of course, that solutions other than aqueous tri-potassium phosphate may be used to remove Hi5: for example, a tri-ethanolamine solution, an alkali phenolate solution, etc. may be used.

It is one feature of this invention that high pressures are not required in either the initial operation in which a tertiary bass olefin is converted to the corresponding tertiary mercaptan, or in the subsequent operation in which the said mercaptan is decomposed to said olefin. On the contrary, pressures varying from atmospheric to about 50 pounds per square inch are used in the initial operation. In order that the initial operation be carried out in the vapor phase, it is necessary that the pressure be less than that pressur at which liquefaction of the hydrocarbon would occur at the operating temperature. It will readily be seen that the use of pressures from about atmospheric to about tour atmospheres are not such as to require the use of expensive high-pressure reaction chambers. Atmospheric pressure, however, is preferred for use in the aforesaid subsequent operation.

It will be observed from the data in the table that a tertiary mercaptan decomposes more readily to the corresponding tertiary base olefin when subjected to a thermal treatmentrwith or with- As indicated above, the proportions oi react- 6 out a catalyst of the type shown-than does the ants, hydrocarbons and hydrogen sulfide can be corresponding monosulilde or a polymer or said varied considerably in the initial operation. Theolefin and that said monosulfide decomposes oretically, the optimum molar ratio of tertiary more readily than said polymer. It will also be base olefin, contained in the hydrocarbon mixapparent that all of these materials decompose ture, to hydrogensulfide would be 1:1. In some 19 more readily when a catalyst of the type shown cases, however, more complete conversions of the is present, than when heat alone is used. The tertiary base olefin to the corresponding tertiary data also demonstrate the importance of temmercaptan are obtained when a slight excess is perature in the method contemplated herein. used. Tertiary base oleflns are notorious for From the foregoing description and examples, their tendency to polymerize and this polymerit should be clear that the present method is an ization reaction tends to complete with the addieffective means for obtaining substantially pure tion reaction, with the resultant formation of tertiary base oleflns from hydrocarbon mixtures high boiling, poly-tertiary base olefins. An excontaining one or more of such oleiins. The prescess of hydrogen sulfide, therefore, will increase ent method, therefore, provides a convenient the conversion oi said olefin to the correspond- 20 mean for obtaining pure tertiary base oleflns ing mercaptan by afiording greater opportunity which are useful in the preparation of organic for the tertiary base olefin-hydrogen sulfide rechemicals, synthetic fuels, elastomers, resins, etc. action. The present method is currently of particular While it is possible, and is contemplated herevalue in. providing pure isobutylene for the manuin, to use the catalyst without a catalyst supfacture of "butyl rubber" and certain synthetic port in the initial operation, it is preferred that fuels. the catalyst be supported on an adsorbent inert It is to be understood that this invention is not carrier. Many such substances may be used for limited to the foregoing illustrative examples but this purpose, typical of which are wood charis to be broadly interpreted as a method oi sepcoal, cocoanut charcoal, granulated coke, cerarating a tertiary base olefin from hydrocarbon tain clays which are catalytically inactive in said mixtures by selectively converting a tertiary base initial operation (as opposed to active non-plasolefin, through the agency of an inorganic comtic clays), silica gel, etc. Correspondingly, it is pound such as hydrogen sulfide to compounds preferred that one of the catalysts, discussed which are susceptible of reversion or decomposihereinabove, be similarly supported when the tion to said tertiary base olefin, separating said tertiary mercaptan is decomposed to the correcompounds from the reaction mixture containing sponding tertiary base olefin in the aforesaid the unconverted hydrocarbons present in the subsequent operation. original hydrocarbon mixtures, reconverting or In the following table, data is presented to decomposing said compounds to said tertiary base demostrate the influence oi temperature upon the olefin and isolating the latter as a substantially decomposition of a typical tertiary mercaptan, pure compound. tertiary butyl mercaptan, obtained as indicated It is to be understood that the present invenhereinabove, and upon related products-tertiary tion is not to be limited to the foregoing typical butyl monosulfide and di-isobutylene-which are illustrative examples of the same, but is to be also obtained in small quantities in the treatment construed broadly as defined by the language of of isobutylene with H25. The decomposition of the appended claims. each individual compound was effected in a re- We claim: actor comprising a glass tube (inside diameter 42 1. The method of purifying a tertiary base olemm.) containing a contact material as indicated fin containing a non-tertiary base olefin hydroin the table, and each reaction product was worked carbon as a contaminant which comprises: conup by removing hydrogen sulfide and unreacted tacting an admixture of said contaminated termaterial with aqueous caustic solution, and drytiary base olefin and hydrogen sulfide in the vaing isobutylene, as described hereinabove. per phase for a short contact time with a catalyst Table I Contact 05 Del,

IIVBI'S DI] Material charged Contact material g g g'faf 2:3. 3%9" tglizolzgttlgl- Pass) THERMAL DECOMPOSITION Tertiary butyl mercaptan... 44 252 6,4

Do as 324 53.6

Do as m 93.5 Di-teriiary butyl sulfide. 51 427 32. 8

Do 42 594 can Dlisobutylene 43 427 7. 0

CATALY'IIU DECOMPOSITION Tertiary butylmercaptan Cocoanut charooalimpregnatedwith equnlwt.0iH P0 1,000 (m grins)... 42 160 23.0

Do do .dO 44 2i? 8i). 7 Dl-tertiary hutyl sulfide 316 (Si. 3

Do so 421 10.0 Diisohutflene- 62 316 36. 9

Do or m 11.2

which promotes the selective conversion of said tertiary base olefin to the corresponding tertiary mercaptan; separating the said tertiary mercaptan from the reaction mixture obtained by the initial operation; decomposing said tertiary mercaptan to the said tertiary base olefin; and separating said tertiary base olefin from the decomposition mixture formed in the last-mentioned operation, thereby obtaining a substantially pure tertiary base olefin.

2. The method of separating a tertiary base olefin from a hydrocarbon mixture containing said olefin which comprises: contacting an admixture of said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with a catalyst which promotes the selective conversion of said tertiary base olefin with hy-' drogen sulfide to the corresponding tertiary mercaptan at a selective conversion temperature; separating said tertiary mercaptan from the reaction mixture obtained by the initial operation; decomposing said tertiary mercaptan to said tertiary base olefin at a temperature in excess 01' the optimum selective conversion temperature of the initial operation and less than the decomposition temperature of the said tertiary base olefin; and separating said tertiary base olefin from the decomposition mixture formed in the last-mentioned operation.

3. The method of separating a tertiary base olefin from a hydrocarbon mixture containing said olefin which comprises: contacting an admixture of said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with a catalyst which promotes the selective conversion of said tertiary base olefin with hydrogen sulfide to the corresponding tertiary mercaptan at a selective conversion temperature; separating said tertiary mercaptan from the reaction mixture obtained by the initial operation; decomposing said tertiary mercaptan to said tertiary base olefin in the presence said catalyst at a temperature in excess of the optimum selective conversion temperature of the initial operation and less than the decomposition temperature of the said tertiary base olefin; and separating said tertiary base olefin from the decomposition mixture formed in the last-mentioned operation.

4. The method of separating a tertiary base olefin from a hydrocarbon mixture containing said olefin which comprises: contacting an admixture or said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time, from about several seconds to several minutes, with a catalyst which promotes the selective conversion of said tertiary base olefin with hydrogen sulfide to the corresponding tertiary mercaptan at a selective conversion temperature; separating said tertiary mercaptan from the reaction mixture obtained by the initial operation: decomposing said tertiary mercaptan to said tertiary base olefin in the presence or said catalyst at a temperature in excess or the optimum selective conversion temperature of the initial operation and less than the decomposition temperature of the said tertiary base olefin: and separating said tertiary base olefin from the decomposition mixture formed in the last-mentioned operation.

5. The method of separating a tertiary base olefin from a hydrocarbon mixture containing said olefin which comprises: contacting an admixture of said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with a catalyst which promotes the selective conversion of said tertiary base olefin with hydrogen sulfide to the corresponding tertiary mercaptan at a selective conversion temperature; separating said tertiary mercaptan from the reaction mix ture obtained by the initial operation; thermally decomposing said tertiary mercaptan to said tertiary base olefin at a temperature in excess of the optimum selective conversion temperature of the initial operation and less than the decomposition temperature of the said tertiary base olefin; and separating said tertiary base olefin from the decomposition mixture formed in the last-mentioned operation.

6. The method of separating a tertiary base olefin from a hydrocarbon mixture containing said olefin which comprises: contacting an admixture of said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a brief contact time, from about several seconds to several minutes, with a catalyst which promotes the selective conversion of said tertiary base olefin with hydrogen sulfide to the corresponding tertiary mercaptan at a selective conversion temperature; separating said tertiary mercaptan from the reaction mixture obtained bythe initial operation: thermally decomposing said tertiary mercaptan to said tertiary base olefin at a temperature in excess of the optimum selective conversion temperature of the initial operation and less than the decomposition temperature of the said tertiary base olefin; and separating said tertiary base olefin from the decomposition mixture formed in the last-mentioned operation.

7. The method of separating a tertiary base olefin from a hydrocarbon mixture containing said olefin which comprises: contacting an admixture of said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with phosphoric acid at a temperature between about 25" C. and about C., thereby selectively converting said tertiary base olefin to the corresponding tertiary mercaptan; separating said tertiary mercaptan from the reaction mixture obtained by the initial operation; decomposing said tertiary base mercaptan to said tertiary base olefin at a temperature in excess oi the optimum temperature of the initial operation and less than the decomposition temperature of the said tertiary base olefin; and separating said tertiary base olefin from the decomposition mixture formed in the last-mentioned operation.

8. The method of separating isobutylene from a hydrocarbon mixture containing said isobutylene which comprises: contacting an admixture of said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with phosphoric acid at a temperature between about 25 C. and about 175 C., thereby selectively converting said isobutylene to tertiary butyl mercaptan; separating said mercaptan from the reaction mixture obtained in the initial operation; decomposing said mercaptan to isobutylene at a temperature in excess of the optimum temperature of the initial operation and less than the decomposition temperature of isobutylene; and separating isobutylene from the decomposition mixture formed in the last-mentioned operation.

9. The method of separating isobutylene from a hydrocarbon mixture containing said isobutylene which comprises: contacting an admixture of said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with phosphoric acid at about '75 C., thereby selectively converting said isobutylene to tertiary butyl mercaptan; separating said mercaptan from the reaction mixture obtained in the initial operaasacms tion; decomposing said mercaptan to isobutylene at a temperature in excess of about 150 C. and

less than the decomposition temperature isobutyiene; and separating isobutylene from the decomposition mixture formed in the last-mentioned operation.

10. The method of separating isobutylene from a hydrocarbon mixture containing said isobutylone which comprises: contacting an admixture c! said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with phosphoric acid at a temperature between about 25 C. and about 175 0., thereby selectively convetting said isobutylene to tertiary butyl mercaptan; separating said mercaptan irom the reaction mixture obtained in posing said mercaptan to isobutylene in the presence of said catalyst at a temperature in excess or the optimum temperature of the initial operation and less than the decomposition temperature of isobutylene; and separating isobutylene irom the decomposition mixture formed in the lastmentioned operation.

11. The method or separating isobutylene from a hydrocarbon mixture containing said isobutylone which comprises: contacting an admixture oi said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with phosphoric acid at about 75 0., thereby selectively converting said isobutylene to tertiary butyl mercaptan; separating said mercaptan from the reaction mixture obtained in the initial operation; decomposing said mercaptan to isobutylene in the presence of said phosphoric acid at a temperature in excess of about 150 C. and less than the decomposition temperature or isobutylene; and separating isobutylene from the decomposition mixture iormed in the last-mentioned operation.

12. The method of separating isobutylene from a hydrocarbon mixture containing said isobuylone which comprises: contacting an admixture of said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with phosphoric acid at about 15 0., thereby selectively converting said isobutylene to tertiary butyl mercaptan; separating said mercaptan from the reaction mixture obtained in the initial operation: thermally decomposing said mercaptan to isobutylene at a temperature of about 300 C. and less than the decomposition temperature oi isobutylene; and separating isobutylene from the decomposition mixture formed in the last-mentioned operation.

13. The method of separating a tertiary base olefin from a hydrocarbon mixture containing said olefin which comprises: contacting an admixture of said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with a catalyst which promotes the selective conversion of said tertiary base olefin with hydrogen sulfide to the corresponding tertiary mercaptan at a selective conversion temperature; separating unchanged hydrocarbons of said hydrocarbon mixture and hydrogen sulfide from the reaction mixture obtained by the initial operation, and thermally decomposing the remainder at said reaction mixture containing said tertiary mercaptan at a temperature in excess of the optimum selective conversion temperature 01' the initial operation and less than the decomposition temperature of the said tertiary base olefin; and separating said tertiary base olefin from the decomposition mixture formed in the last-mentioned operation.

the initial operation; decom- 14. The method of separating a tertiary base olefin from a hydrocarbon mixture containing said olefin which comprises: contacting an admix-' ture of said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with a catalyst which promotes the selective conversion of said tertiary base olefin with hydrogen sulfide to the corresponding tertiary mercaptan at a selective conversion temperature; separating unchanged hydrocarbons or said hydrocarbon mixture and hydrogen sulfide from the reaction mixture obtained by the initial operation, and decomposing the remainder of said reaction mixture containing tertiary mercaptan in the presence of said catalyst, at a temperature in excess 01' the optimum selective conversion temperature or the initial operation and less than the decomposition temperature of the said tertiary base olefin: and separating said tertiary base olefin from the decomposition mixture formed in the last-mentioned operation.

15. The method of separating a tertiary base olefin i'rorn a hydrocarbon mixture containing said olefin which comprises: contacting an admixture of said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with a catalyst which promotes the selective conversion of said tertiary base olefin with hydrogen sulfide to the corresponding tertiary mercaptan, tertiary sulfide and tertiary base olefin polymer, at a selective conversion temperature: separating said tertiary mercaptan, tertiary sulfide and tertiary base olefin polymer from the reaction mixture obtained by the initial operation; concurrently decomposing said tertiary mercaptan, tertiary sulfide and tertiary base olefin polymer to said tertiary base olefin at a temperature in exseas of the optimum selective conversion temperature of the initial operation and less than the decomposition temperature of the said tertiary base olefin; and separating said tertiary base olefin from the decomposition mixture formed in the last-mentioned operation.

16. The method of separating a tertiary base olefin from a hydrocarbon mixture containing said olefin which comprises: contacting an admixture oi! said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with a catalyst which promotes the selective conversion of said tertiary base olefin with hydroen sulfide to the corresponding tertiary mercaptan tertiary sulfide and tertiary base olefin polymer, at a selective conversion temperature; separating said tertiary mercaptan, tertiary sulfide and tertiary base olefin polymer from the reaction mixture obtained by the initial operation; concurrently decomposing said tertiary mercantan, tertiary sulfide and tertiary base olefin polymer to said tertiary base olefin in the presence of said catalyst at a temperature in excess of the optimum selective conversion temperature or the initial operation and less than the decomposition temperature of the said tertiary base olefin; and separating said tertiary base olefin from the decomposition mixture formed in the last-mentioned operation.

17.'I'he method of separating a tetriary base olefin from a hydrocarbon mixture containing said olefin which comprises: contacting an admixture or said hydrocarbon mixture and hydrogen sulfide in the vapor phase for a short contact time with a catalyst which promotes the selective conversion or said tertiary base olefin with hydrogen sulfide to the corresponding tertiary mercaptan, tertiary sulfide and tertiary base olefin polymer, at a selective conversion temperature: separating said tertiary mercaptan, tertiary sulfide and tertiary base olefin polymer from the reaction mixture obtained by the initial operation; concurrently, thermally decomposin said tertiary mercaptan, tertiary sulfide and tertiary base olefin polymer to said tertiary base olefin at a temperature in excess of the optimum selective assume conversion temperature of the initial operation and less than the decomposition temperature of the said tertiary base olefin; and separatingsaid tertiary base olefin from the decomposition mixture formed in the last-mentioned operation. DARWIN E. BADERTSCHER. DUNCAN J. CROWIEY; CHARLES F. FEASLEY.

Certificate 0! Correction Patent N 0. 2,386,773.

October 16, 1945.

DARWIN E. BADERTSCHER ET AL. It is hereby certified that errors appear in the printed specification of the above numbered line 21, for "(2) (H C) CS umn, line 47, for clorlde read compete; line 40, for

ale

demostrate the record of the case in the Patent Office.

patent requiring correction as follows: teritalg read tertiary; p e 3, second column, line 37, strike out (C read chloride; page 7, first column, line 16, or complete read demonstrate; and that the said Letters Patent should be read with these corrections therein that the same may Page 2, first column,

+ H 8"; pa e 5, first colconform to Signed and sealed this 9th day of April, A. D. 1946.

LESLIE FRAZER,

First Assistant Oommissioner of Patents.

olefin polymer, at a selective conversion temperature: separating said tertiary mercaptan, tertiary sulfide and tertiary base olefin polymer from the reaction mixture obtained by the initial operation; concurrently, thermally decomposin said tertiary mercaptan, tertiary sulfide and tertiary base olefin polymer to said tertiary base olefin at a temperature in excess of the optimum selective assume conversion temperature of the initial operation and less than the decomposition temperature of the said tertiary base olefin; and separatingsaid tertiary base olefin from the decomposition mixture formed in the last-mentioned operation. DARWIN E. BADERTSCHER. DUNCAN J. CROWIEY; CHARLES F. FEASLEY.

Certificate 0! Correction Patent N 0. 2,386,773.

October 16, 1945.

DARWIN E. BADERTSCHER ET AL. It is hereby certified that errors appear in the printed specification of the above numbered line 21, for "(2) (H C) CS umn, line 47, for clorlde read compete; line 40, for

ale

demostrate the record of the case in the Patent Office.

patent requiring correction as follows: teritalg read tertiary; p e 3, second column, line 37, strike out (C read chloride; page 7, first column, line 16, or complete read demonstrate; and that the said Letters Patent should be read with these corrections therein that the same may Page 2, first column,

+ H 8"; pa e 5, first colconform to Signed and sealed this 9th day of April, A. D. 1946.

LESLIE FRAZER,

First Assistant Oommissioner of Patents. 

